Department of Physics, McNeese State University, Lake Charles, Louisiana 70609, USA.
J Phys Chem A. 2013 Feb 14;117(6):1310-8. doi: 10.1021/jp307467j. Epub 2012 Nov 1.
Using density functional theory based calculations, we have systematically studied the equilibrium geometries, relative stabilities, and electronic and magnetic properties of Fe and Mn atoms interacting with a varying number of BO(2) moieties. These clusters are found to exhibit hyperhalogen behavior with electron affinities as high as 6.9 eV once the number of BO(2) moieties exceed the nominal valences of these transition metals toms, namely 2 for both Fe and Mn. In all cases the transition metal atoms retain a sizable spin magnetic moment, even exceeding their free atom values at certain compositions. We also note that when more than two BO(2) moieties are bound to neutral Fe and Mn atoms, they tend to dimerize. In the case of negative ions, this process occurs at n ≥ 3, thus leading to different neutral and anionic ground state geometries. The effect of these structural changes in the interpretation of photoelectron spectroscopy experiments is discussed.
利用基于密度泛函理论的计算方法，我们系统地研究了与不同数量的 BO(2) 基团相互作用的 Fe 和 Mn 原子的平衡几何形状、相对稳定性以及电子和磁性性质。这些团簇表现出超卤素行为，电子亲和能高达 6.9eV，一旦 BO(2) 基团的数量超过这些过渡金属原子的标称价数，即 Fe 和 Mn 的 2。在所有情况下，过渡金属原子都保持相当大的自旋磁矩，甚至在某些组成下超过其自由原子值。我们还注意到，当超过两个 BO(2) 基团与中性 Fe 和 Mn 原子结合时，它们往往会二聚化。对于负离子，这个过程发生在 n ≥ 3，从而导致不同的中性和阴离子基态几何形状。讨论了这些结构变化对光电子能谱实验解释的影响。
